Films of the Tl‐Ba‐Ca‐Cu‐O high‐Tc superconductor can be prepared by several organometallic chemical vapor deposition routes. Two of these involve Ba‐Ca‐Cu‐0 films that are first prepared using the volatile metal‐organic precursors Ba(heptafluorodimethyloctanedionate)2, Ca(dipivaloylmethanate)2, and Cu(acetylacetonate)2‐ Deposition is carried out at a pressure of 5 Torr with argon as the carrier gas and water vapor as the reactant gas. Thallium is next incorporated into these films either by organometallic chemical vapor deposition using Tl(cyclopentadienide) as the source, or by vapor diffusion using bulk Tl‐Ba‐Ca‐Cu‐O as the source. Thallium deposition is carried out at atmospheric pressure with an argon carrier and water‐saturated oxygen reactant gas, followed by rapid thermal annealing. Both procedures yield films that consist primarily of the TlBa2Ca2Cu3Ox phase, have preferential orientation of the Cu‐O planes parallel to the substrate surface, and exhibit onset of superconductivity at ∼125 K with zero resistance by 100 K.